(AMINOETHINYL)METALLIERUNGEN. VII. SYNTHESE UND REAKTIVITAET VON (3-STANNYLOXY-3-ALKEN-1-INYL)AMINEN

Article abstract of DOI:10.1016/S0022-328X(00)93759-8

The C=O double bond of diphenylketene inserts into the tin-acetylenic carbon single bond of β-stannylated ynamines.The formation of 4,4-diphenyl-3-stannyloxy-3-buten-1-ynyl amines is proved partly by spectroscopic data, partly by isolation.Under detachment of the stannyl group they hydrolyze relatively easily to the corresponding acyl ynamines and react with acyl chlorides to give the corresponding 3-acyloxyenynamines.N-Methyl-N-(4,4-diphenyl-3-triphenyl-stannyloxy-3-buten-1-ynyl)aniline yields under the conditions of chromatography on silica gel a destannylated β-naphthol derivative; the same enynamine isomerizes in CDCl3 solution spontaneously to 4-(N-methylanilino)-1-phenyl-3-triphenylstannyl-2-naphthol, the structure of which is established by an X-ray analysis.The reaction of the β-stannylated ynamines with ketene or dimethyl-ketene directly gives the corresponding acyl ynamines, which are characterized by the reaction with tosylazide as crystalline diazo compounds.By addition of an excess of ketene the 2-acetyl-3-amino-2-cyclobuten-1-ones are formed as 1:2 adducts.